Durable fluorochemical-melamine resin textile finish



United States Patent Office 3,087,905 Patented Apr. 30, 1963 3,087,905 DURABLE FLUOROCHEMICAL-MELAMINE RESIN TEXTILE FINISH Linton A. Flock, Bridgewater Township, Somerset County, N.J., assignor to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Filed May 3, 1960, Ser. No. 26,402. 8 Claims. (Cl. 260-29.4)

The present invention relates to a durable textile finishing composition for textile materials and, more particularly, it relates to a durable textile finishing composition which imparts wrinkle recovery, water-repellency and oilrepellency to the cellulosic textile materials finished therewith. Further, the invention relates to the process for applying such a finishing composition to textile materials and to the finished textile materials themselves.

A variety of compositions have heretofore been proposed as water and/or oil-repellent textile finishes. Many of these finishes are not both hydrophobic and oleophobic. Further, most of these finishes are not durable and lose their repellent properties When subjected to laundering or dry cleaning operations.

A comparatively recent addition to the group of water and oil-repellent chemicals is a class of compounds sometimes identified as fluorochemicals. In general, these are perfluoro or heavily fluorinated long chain aliphatic compounds which, when applied to fabrics such as wool and silk, are claimed to impart Water and oil repellency thereto. This repellency is durable to dry cleaning but in general is not durable to laundering operations. These fluorochemicals have been applied to cellulosic fabrics but with comparatively little success in that they are characterized by comparatively poor durability to washing operations. In general, textiles treated with these fluorochemicals resist water and oil borne stains, in addition to being water repellent.

An object of the present invention is to provide a composition which when applied to cellulosic textile materials will provide a water and oil repellent finish thereto that is durable to both laundering and dry cleaning.

It is a further object of the present invention to provide a composition that will impart in addition to oil and water repellency, wrinkle recovery or resistance to cellulosic materials.

A further object of the present invention is to provide a process for applying such compositions to textile materials and to provide textile materials characterized by the properties above identified.

According to the present invention, a process is provided for imparting an oil and Water repellent finish to textile materials that is durable to dry cleaning and laundering which comprises applying thereto from between .1% and of an oleophobic and hydrophobic fluorochemical and from between 1% and 25% of a water- 'soluble triazine-aldehyde resin thereto and thereafter curing the applied material to a water insoluble state on the fabric in the presence of a curing accelerator.

By fluorochemicals as that and similar expressions are employed herein, it is meant oleophobic and hydrophobic heavily fluorinated long chain aliphatic compounds which, When applied to cellulosic textile materials, impart Water and oil repellency thereto.

A particular group of fiuorochemical compounds specifically contemplated are those having the following general formula:

in which x is a value between 3 and 13 inclusive, R is lower alkyl, such as methyl, ethyl, propyl, butyl and the like, having from 1-6 carbon atoms, R is alkylene containing from 1-12 carbon atoms and R is H, methyl or ethyl. These compounds may be prepared in accordance with the disclosure set forth in U.S. Patent 2,803,615.

By the term textile material and similar expressions as they are employed herein, it is meant fibers, filaments, yarns, fabric, whether Woven or non-woven, knitted, felted or otherwise formed of natural fiber, including those of vegetable or animal origin or of the so-called synthetics. Thus, the textile material may be cotton, linen, hemp, jute, silk, wool, cellulose acetate, rayon, nylon the polyester fibers such as those prepared from alkylene glycols and terephthalic acid, the acrylic fibers and so on. The textile materials may comprise mixtures of one or more fibers, of vegetable, animal or synthetic origin.

By cellulosic textile materials or cellulose containing textile materials as these and similar terms are employed in the present specification, it is meant textile materials (fibers, filaments, yarns, fabrics, Whether woven or non-woven, knitted, felted or otherwise formed) containing at least 50% of cellulose fiber such as cotton, rayon, linen, hemp, jute or the like. The cellulose fibers may be present in combination with other natural or synthetic fibers such as wool, acetate, nylon, polyester fibers, acrylic fibers and the like. Preferably, the textile material is a formed, woven, cotton fabric.

By the term triazine-aldehyde resin as that term is employed herein, it is meant the aldehyde and, in particular formaldehyde condensates, of the compounds disclosed in U.S. Patent 2,197,357 and in particular the potentially thermosetting water-soluble aldehyde condensates of melamine and guanamine as well as substituted derivatives thereof. With respect to guanamine-formaldehyde con densates, those described in U.S. Patent 2,887,409 are particularly contemplated. The triazine-aldehyde condensates may be employed singly or in combination with one another.

The term triazine-aldehyde resin" or condensate also includes the alkylated or etherified derivatives of triazinealdehyde condensates, in which the alcohol is a monohydric aliphatic alcohol such as methyl, ethyl, propyl, butyl and the like, polyols, such as the glycols, for example, ethylene glycol, propylene glycol and the like, the glycol ethers and other alcohols known as alkylating agents by those skilled in the art.

Further, the term triazine-aldehyde resins includes mixtures of triazine-aldehyde condensates in combination with other aminoplast resins Where in such combinations, the triazine-aldehyde condensate constitutes at least about 25% on a weight basis of the total aminoplast resin. Preferably, the total aminoplast contains at least 50% by weight of triazine-aldehyde resin.

As examples of suitable triazine-aldehyde resins that may be employed, the melamine formaldehyde condensates are the single most important class. Suitable melamine-aldehyde condensates include those having from 1 to 6 moles of combined formaldehyde and from 1 to 6 moles of combined alcohol, such as for example methyl, ethyl and the like, although in addition to aliphatic monohydric alcohols, polyhydric alcohols or polyol's such as the glycols and ether alcohols are also contemplated. Examples of such resins and how they are prepared may be found in U.S. Patent 2,197,357 and U.S. Patent 2,529,- 856. These resins are preferably water soluble or water dispersible and may be characterized as being essentially monomeric potentially thermosetting materials. Examples of suitable melamine-aldehyde condensates inelude tris(methoxymethyl) melamine, tris(methoxymethyl) dimethylol melamine, hexakis'(methoxymethyl) melamine and the like. Another important class of triazine-aldehyde resins is the guanamine aldehyde condensates, also disclosed in U.S. Patent 2,197,357, among 3 numerous other places, including U.S. Patent 2,385,766, U.S. Patent 2,461,939 and U.S. Patent 2,887,409 The guanamine-aldehyde condensate disclosed there and their alkylated derivatives are a preferred group of guanarnines. These include the formaldehyde condensates of methoxyacetoguanamine, ethoxyacetoguanamine, tertiary butoxyacetoguanamine, cyanopropoguanamine and the like.

Among the other aminoplast resins contemplated for use in combination with the triazine-aldehyde condensates are urea and thiourea formaldehyde condensates such as dimethylol urea, alkylated such as methylated dimethylol urea and thiourea, dimethylol ethylene urea, dimethylol ethylene thiourea, dimethylol 1,2-propylene urea and thiourea, dimethylol 1,3-propylene urea and thiourea and other related homologous compounds. Additionally, the formaldehyde condensates of dicyandiamide, biuret and the like are contemplated as are the water soluble formaldehyde condensates of thiobisamides such as are described in U.S. Patent 2,887,408.

Urons, such as for exampl NN-bis(methoxymethyl) uron and various other and closely related compounds such as are described in U.S. Patent 2,373,135 are contemplated. Additionally, tetrahydrotriazones such as are described in U.S. Patent 2,373,135 are contemplated. Additionally, tetrahydrotriazones such as tetrahydro-S- (beta-hydroxyethyl)-5-triazone and related compounds that are described in U.S. Patent 2,304,624 are contemplated.

These exemplary aminoplasts suited for use with the triazine-aldehyde resins may be employed singly or in combination with one another, in combination with said triazine-aldehyde resins.

The fluorochemicals and the triazine-aldehyde resins are preferably applied from a single application bath such as is normally employed in the textile finishing industry. However, the composition may be applied by dipping, spraying, immersing or other suitable means known to those skilled in the art.

As indicated, they are preferably applied simultaneously from a single pad bath solution where they are present in such amounts and the application is so carried out that from between .1% and 5% of the fluorochemical and from between 1 and 25% of the water-soluble triazinealdehyde resin is applied to the textile material based on its dry weight. For most applications, and preferably, the fluorochemical is applied of from between .25 and 1% and the triazine-aldehyde is applied in amounts of from between 2 and based on the dry weight of the textile material.

It is an important aspect of this case that stable compatible compositions of the triaZine-aldehyde resin and fluorochemical can be prepared. Thus, in accordance with this invention, a suitable stable aqueous solution or emulsion is provided which contains the fluorochemical and triazine-aldehyde resin in relative amounts by weight of from between 1 and 50 parts of the fluorochemical and from between 10 and 250 parts of the water-soluble aminoplast resins.

In the process aspect of this invention, the composition containing the fluorochemical and the aminoplast resin is normally applied to the textile material in the presence of a suitable accelerator or catalyst to promote the cure of the triazine-aldehyde resin. The catalyst or curing accelerator is one normally employed with aminoplast resins and include the ammonium salts, like ammonium chloride, amine salts like triethylamine hydrochloride, alkanolamine salts like triethanolamine hydrochloride, metal salts such as magnesium, zinc and aluminum chloride and the like, free acids like oxalic, tartaric and the like. These catalysts may be employed singly or in com bination with one another. Catalyst concentrations may vary widely, depending upon the nature of the catalyst itself. The range of catalyst may be from between about /2 to 25% and in certain limited instances, higher, based on the weight of the triazine-aldehyde resin solids employed. More particularly, with ammonium salts such as ammonium sulfate, it may vary from about /2 to about 7.5% based on the weight of triazine-aldehyde resin solids employed; with metal salts, such as preferred anhydrous magnesium chloride, amounts of between 8 and 20% based on the weight of resin solids is the preferred operating range. With amine or alkanolamine salts such as isopropanolamine hydrochloride from between about 1 to about 10% catalyst concentration based on the weight of resin solids employed is preferred.

After application, the treated textile material is dried and cured, for times and temperatures normally required to effect a suitable cure for triazine-aldehyde resins on textile materials. As is well known, the times and temperatures required to effect such cures vary inversely. Thus, as the temperature increases, the time of cure decreases and vice versa. Preferably, the treated fabric is cured at temperatures of from between 250 to 450 F. for from 5 to minutes.

Textile materials treated with the compositions of the present invention are in general characterized by the following properties:

(1) Greater water-repellency than that obtained by the use of the fluorochemical alone,

(2) Greater durability of water and oil-repellent finish to laundering, and

(3) On cellulosic textile material, better wrinkle recovery than obtained with the triaZine-aldehyde resin alone.

In order that the present invention may be more fully understood, the following examples are given primarily by way of illustration. No details or enumerations contained therein should be construed as limitations on the present invention except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specifically designated.

EXAMPLE 1 A non-ionic stabilized emulsion of fluorochemical A was prepared. Fluorochemical A is a fluorochemical of the type set forth in general formula above in which x is 7, R is propyl, R is C H and R is H. The said aqueous emulsion contained 7% of fluorochemical A (2% solids at 28-30% real solids), .1% of sodium acetate, 6.25% of isopropyl alcohol and .02% of a non-ionic surface active agent having a molecular weight of 2900, that is a condensate of polyoxypropylene and ethylene oxide.

Three pad baths were prepared, the first containing 1.25% of the fluorochemical A emulsion described above, the second containing 1.25% of the fluorochemical A emulsion in combination with 6.25% solids of triazine-aldehyde resin 1 and in the third bath 1.25% of fluorochemical A emulsion in combination with 6.25% solids of triazine-aldehyde 2. Triazine-aldehyde resin 1 is a partially methylated trimethylol melamine and triazine-aldehyde resin 2 is a substantially fully etherified substantially fully methylolated melamine-ethylene urea formaldehyde resin containing 75% by weight of triazinealdehyde resin on total resin solids basis. With triazinealdehyde resins 1 and 2, 12% of magnesium chloride based on the weight of resin solids was employed as a curing accelerator. In addition, pad baths containing triazine-aldehyde resins 1 and 2 containing 12% of magnesium chloride as accelerator were also prepared.

Applications of the above baths were made on x 80 cotton percale using a standard padding procedure with an 80% wet pick-up. The treated fabrics were dried at 225 F. for 1 minute and cured at 350 F. for 1.5 minutes. The treated fabrics contained 1% solids of fluorochemical A and 5% solids of triazine-aldehyde resins 1 and 2 respectively.

The wrinkle recovery of the treated fabric was measured on a Monsanto wrinkle recovery tester following Appearance of Fabric no wetting of upper surface.

slight wetting of upper surface.

wetting of upper surface at spray points. partial Wetting of whole upper surface.

complete wetting of whole upper and lower surfaces.

The oil repellency of the treated fabrics was measured by applying a drop of various mixtures of mineral oil and heptane to the fabric, and after three minutes noting the mixture richest in n-heptane which does not penetrate the fabric. a The repellency is rated as follows.

Heptane: Oil

Mixture Not Penetrating (VOL/Vol.)

Rating The washes were carried out in a Laundromat washer using Water at 140 F. and 0.01% of neutral soap with a wash cycle of 20 minutes. After rinsing, the fabrics were pressed dry.

The dry cleaning was carried out by the procedure described on page 146 of the 1957 edition of the Technical Manual and Year Book of the American Association of Textile Chemists and Colorist.

Results of the tests are shown in Table I.

Table l A B O D E F Fluorcchemical A percent. 1 1 1 Triazine-Aldehyde Resin 1 percent" 5 Triazine-Aldehyde Resin 2 percent 5 5 Wrinkle recovery:

W+F, degrecs.. 155 248 262 230 247 c. 145 Water repellency;

Initial 70 80 80 0 0 After washing 0 90 90 0 0 After 3 dry cleaningsw. 80 90 S0 0 0 Oil repellency:

Initial 90 100 100 0 0 After washing 0 90 90 0 0 After 3 dry cleanings.-. 100+ 100+ 90 0 0 A review of Table I above discloses several surprising and unexpected advantages of the present invention. Thus, only applications B and C are durable to washing, but not only are they durable, but it will be seen that the combination of the triazine-aldehyde and fluorochemical produces better water and oil repellency than the fluorochernical alone, and better wrinkle recovery than the triazine-aldehyde resin alone. This is quite surprising, for comparing A and F it will be seen that the application of the fluorochemical alone imparts substantially no wrinkle recovery and it would be expected from the nature of such compounds, that their presence would adversely affect wrinkle recovery. Since the triazine-aldehyde resin confers no water or oil repellency of itself, it is surprising that combinations containing the same have improved initial water and oil repellency and durable water and oil repellency. Table I further demonstrates that the finish of this invention is durable to dry cleaning.

6 EXAMPLE 2 The procedure of Example 1 was repeated, substituting cotton poplin for the cotton percale.

The results are shown in Table II.

Table II A B O D E F Fluorochemical A percent 1 1 1 Triazine-aldehyde Resin 1 percent 5 5 Trlazine-aldehyde Resin 2 percent 5 5 Wrinkle recovery:

W+F, degrees 167 248 208 239 251 120 Water repellency:

Initial 90 0 0 After washing 70 90 90 0 0 Oil repellency:

Initial 100+ 100 90 0 0 After washing 50 100 90 0 0 A review of Table 11 above Wlll demonstrate that the synergistic effects achieved with respect to the finish of this invention on cotton percale is also found on cotton poplin. While it appears that water repellency and oil repellency of 'Fluorochemical A on cotton poplin is more durable than on cotton percale, it should be noted that the durability of water repellency and oil repellency is greatly enhanced by employing the composition of this invention.

EXAMPLE 3 Pad bath A containing 2.1% of fluorochemical A (.63 solids at 28-30% solids), 8% isopropyl alcohol, .01% of a non-ionic surface active agent (an alkarylpolyether alcohol containing 1 mole of nonylphenol and 9.5 moles of ethylene oxide) and .05 of sodium acetate.

Pad bath B contained 3.8% solids of a commercially available Water repellent containing a blend of a partially methylated trimethylol melamine and methylol stearamide (of the type described in U .S. Patent 2,357,273) and 1% of ammonium sulfate as a'curing accelerator.

Pad bath C contained 2.1% of fluorochemical A (.63% solids at 28-30% solids), 8% of isopropyl alcohol, .01% of a non-ionic surface active agent (an alkylaryl-polyether alcohol containing 1 mole of nonylphenol and 9.5 moles of ethylene oxide), 0.5% of sodium acetate and 3.8% solids of the commercial water repellent described with reference to pad bath B and 1% of ammonium sulfate as a curing accelerator.

The pad baths were applied to 80 x 80 cotton percale using a standard padding procedure with an 80% wet pick-up. The treated fabrics were dried at 225 F. for 1 minute and cured at 350 F. for 1.5 minutes. The treated fabrics contained .5% solids of fluorochemical A and/or 3% solids of the commercial water repellent.

The oil repellency of the treated fabric was measured as described in Example 1.

The washes reported were carried out in a home automatic washing machine using neutral soap withwater at F. The dry cleaning was carried out by the procedure described on page 146 of the 1957 edition of the Technical Manual and Year Book of the American Association of Textile Chemists and Colorists.

The results are reported in Table HI below.

A review of Table III above demonstrates that only with the combination employed in pad bath C, namely the commercial water repellent and spot resistant finish and fiuorochemical A is an oil repellent finish imparted to cotton percale which is both durable to washing and dry cleaning. Thus, finishes effected with triazine-aldehyde condensate containing materials such as those described in US. Patent 2,357,273 in combination with the fluorochemicals of this invention are a preferred aspect of this invention.

While the present invention has been described in particular with respect to compositions containing fluorochemicals and triazine-aldehyde resin, other textile finishing agents or auxiliaries may be employed therewith to achieve special effects. Thus, the use of softeners, lubricants, hand modifying thermoplastic resins, dyes and the like in combination therewith are fully contemplated.

I claim:

1. A process for imparting a durable oil and Water repellent finish to textile material which comprises applying thereto from between .1 and inclusive by weight of an oleophobic and hydrophobic fiuorochemical having the following formula:

where x is an integer between 3 and 13 inclusive, R is lower alkyl having from 1-6 carbon atoms inclusive, R is alkylene having from 1-12 carbon atoms inclusive and R is H, methyl or ethyl, and from between 1% and 25% inclusive by weight of a water soluble triazine-aldehyde resin, said percent by weight of fluorochemical and triazine-aldehyde resin being based on the dry weight of the textile material, and thereafter heat curing the applied material to a water insoluble state on the fabric in the presence of a curing accelerator.

2. A process for imparting a durable oil and water repellent finish to textile material which comprises applying thereto a composition comprising from between (1) about .25% and about 1% inclusive by weight of an oleophobic and hydrophobic fiuorochemical having the following general formula:

where x is an integer between 3 and 13 inclusive, R is lower alkyl having from 1-6 carbon atoms inclusive, R is alkylene having from 1-12 carbon atoms inclusive and R is H, methyl or ethyl, (2) between about 2 and about inclusive by weight of a water soluble triazinealdehyde resin, said percent by weight of fluorochemical and triazine-aldehyde resin being based on the dry weight of the textile material and thereafter heat curing the composition in the presence of a curing accelerator to a water insoluble state.

3. A process for imparting a wrinkle resistant oil and water repellent finish to cellulose fabric, durable to dry cleaning and laundering which comprises applying thereto a composition comprising from between (1) about .25 and about 1% inclusive by weight of an oleophobic and hydrophobic fluorochemical having the following general formula:

R1 where x is an integer between 3 and 13 inclusive, R is lower alkyl having from 1-6 carbon atoms inclusive, R is alkylene having from 1 to 12 carbon atoms inclusive and R is H, methyl or ethyl, (2) between about 2 and about 8 10% inclusive by weight of a water soluble triazine-aldehyde resin, said percent by weight of fiuorochemical and triazine-aldehyde resin being based on the dry Weight of the cellulose fabric and thereafter heat curing the composition in the presence of a curing accelerator to a water insoluble state.

4. A process according to claim 3 in which the triazine-aldehyde resin is a melamine-formaldehyde resin.

5. Textile material characterized by an oil and water repellent finish durable to laundering having cured thereon in a Water insoluble state a composition containing between .1 and about 5% inclusive by weight of an oleophobic and hydrophobic fluorochemical having the following formula:

where x is an integer between 3 and 13 inclusive, R is lower alkyl having from 16 carbon atoms inclusive, R is alkylene having from 1-12 carbon atoms inclusive and R is H, methyl or ethyl, and between 1% and 25% inclusive by weight of a water soluble triazine-aldehyde resin, said percent of weight of fluorochemical and triazine-aldehyde resin being based on the dry weight of the textile material.

6. Cellulose textile material characterized by a wrinkle resistant oil and water repellent finish durable to laundering and dry cleaning having cured thereon in a water insoluble state a composition containing (1) about .25 and about 1% inclusive by weight of an oleophobic and hydrophobic fluorochemical having the following general formula:

where x is an integer between 3 and 13 inclusive, R is lower alkyl having from 1-6 carbon atoms inclusive, R is alkylene having from 1-12 carbon atoms inclusive and R is H, methyl or ethyl, and (2) between about 2 and about 10% inclusive by weight of a water soluble triazinealdehyde resin, said percent by weight of fiuorochemical and triazine-aldehyde resin being based on the dry weight of the textile material.

7. Cellulose textile material according to claim 6 in which the triazine-aldehyde resin is a melamine-formaldehyde resin.

8. An aqueous emulsion comprising a fiuorochemical having the following general formula:

1 where x is an integer between 3 and 13 inclusive, R is lower alkyl having from l-6 carbon atoms inclusive, R is alkylene having from 1-12 carbon atoms inclusive and R is H, methyl or ethyl, and a water soluble triazinealdehyde condensate in relative amounts by weight of from between 1 and 50 parts inclusive of the fluorochemical and from between 10 and 250 parts inclusive of the triazine-aldehyde condensate.

References Cited in the file of this patent UNITED STATES PATENTS 2,197,357 Widmer et al Apr. 16, 1940 2,536,050 Fluck Jan. 2, 1951 2,654,720 Cohen et al Oct. 6, 1953 2,777,783 Welch Jan. 15, 1957 2,803,615 Ahlbrecht et al. Aug. 20, 1957 

1. A PROCESS FOR IMPARTING A DURABLE OIL AND WATER REPELLENT FINISH TO TEXTILE MATERIAL WHICH COMPRISES APPLYING THERETO FROM BETWEEN .1 AND 5% INCLUSIVE BY WEIGHT OF AN OLEOPHOBIC AND HYDROPHOBIC FLUOROCHEMICAL HAVING THE FOLLOWING FORMULA: 